TWI286854B - Proton conducting mediums for electrochemical devices and electrochemical devices comprising the same - Google Patents

Abstract

An electrochemical device and a proton conducting medium for use in an electrochemical device having a proton conducting electrolyte comprising the formula: HaMbQ.nH2O. Where H is a proton, M is a cation, Q is the fluoroborate or fluoroheteroborate anion, n ranges from 0.01 to 1000, a ranges from 0.01 to 2 and b ranges from 0 to 2, a and b are chosen to render the formula electrically neutral, and when b is greater than 0, the ratio of b to a is less than 100 to 1.

Description

r 1286854 钃 • EMBODIMENT DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an electrochemical device and a proton conducting medium for use in such an electrochemical device. Prior Art Proton exchange fuel cells, including polymer electrolyte membrane fuel cells, are converted to electrical energy by chemical energy, providing a clean and efficient energy conversion method for power generation. Electrochemical conversion is carried out by introducing an oxygen-containing oxidant gas through a gas diffusion cathode and introducing a hydrogen-containing fuel gas through a gas diffusion anode. Protons migrate into a proton conducting electrolyte medium containing a proton conductor and react with the reduced oxygen to form water. In order to promote chemical conversion, a surface-containing electrode is usually used. Various types of fuel cells have been developed depending on the type of fuel employed, such as helium, natural gas, gasoline, and alcohols; their operating conditions, such as low temperature and high temperature; and the type of proton conducting electrolyte used in fuel cells. Examples of fuel cells include domain fuel cells, polymer-electrolyte-membrane (PEM) fuel cells, acid fuel cells, molten carbonate fuel cells, and solid oxide fuel cells. Low temperature operation of fuel cells (<100 °C) generally requires the use of very pure hydrogen as a source of hydrogen. However, such a hydrogen source is relatively expensive and requires a complicated gas storage device. Hydrogen derived from carbon-based fuels, such as hydrogen from the following water gas changes, hydrogen CO + h2o 〇C〇2 + h2 5 1286854 * 'cheaper and easy to store> However, these fuel sources contain different amounts of oxidized Stone counter, and < 100C, by adsorption at the cathode and anode, 1 〇 ppm level of carbon monoxide will poison the platinum catalyst :). [Proton exchange membrane fuel cells operate at higher temperatures (at least 100 to 25 〇. 〇 significantly reduces the impact of carbon monoxide adsorption. More temperatures may also increase the reaction kinetics and efficiency of fuel cells.) Fuel cell more south temperature The work poses a serious challenge to fuel cell design. One of the challenges of the court is the choice of proton conducting electrolyte. (Proton conducting media used in high temperature working fuel cells should have one or more of the following characteristics: 咼 conductivity, excellent chemical, electrochemical and morphological stability, oxime oxidation, good hydrogen and oxygen solubility, and electrodes Catalyst materials have an optimal interaction.) / Hydrated perfluorinated sulfonic acid polymers, such as Nafi〇nTM (a trademark of DuP〇nt), and similar materials that are also commercially available for general use in low temperature fuel cells Proton conducting electrolyte. However, the proton conduction mechanism φ of the Nafi〇nTM type membrane is based on the migration of hydrated protons, so a fuel cell using a NafionTM membrane requires a complex water management system and is above 1. Pressurize under 〇 conditions. Phosphoric acid cells provide an opportunity to operate fuel cells at high temperatures' but the phosphate anions are strongly absorbed on the platinum electrode. Proton conducting electrolytes having strong adsorption characteristics for platinum catalysts result in loss of the active sites required for oxygen reduction and result in relatively low current densities, reducing the power density of the fuel cell. The following patents and papers represent the current state of the art in the use of proton conducting membranes in fuel cells and electrochemical devices. 6 1286854 US 6,468,684 discloses a solid acid electrolyte of φ ΤΤ η ^ 巧 MaHb(X〇t)c, having a protonated proton, M being a metal D c A genus such as Li, Be, Na and Mg' X is Si, p, S, As, a, b, c^t is a .^ Λ ^ rational number, used as a proton conducting material. Some electrolytes do not require hydration, and can work at temperatures above 1 oo °C. a representative of a class

Composite film made of CsHS04, performance

Conductivity up to 8 ms/cm in 146 ° C humidified air (pH I H20 = 3.13 X 1 〇 2 atmosphere). No. 5,344,722 discloses a cluster of phosphoric acid fuel cells in which the electrolyte comprises phosphoric acid and a fluorinated compound, such as a salt of a nonafluorobutane sulfonate or an anthrone compound, such as, for example, a polyalkyl hydrazine. Alkanes, such as polyfluorenyl oxime 0. In Plenum Press, "Surface Electrochemistry", café price - low price, page 887, J. 〇·Μ· Bockris and S_ υ·Μ·Khan report' The aqueous solution of difluoromethane acid anhydride exhibits a higher oxygen reduction rate on the platinum catalyst than the phosphoric acid solution, presumably because of improved oxygen solubility in the electrolyte and lower adsorption of acid on the surface of the platinum catalyst.

Alberti et al., "S〇lidState I〇nics,, 145 (2〇〇1), pp. 3-16, entitled "Solid Proton Conductors, Current Major Applications and Prospects", discloses various protons for fuel cells. Conductive membrane. Examples of proton conductive materials include: impregnated hydrophilic additives such as heteropolyacids, linoleic acid hammers, sulfated oxidative proton conducting polymers; sulfonated polyether ketones and solids such as perfluorinated sulfonic acid polymers Acid electrolyte.

Yang et al., “Journal of Power Sources” l〇3, (2001), pp. 1-9 titled “Approaches And Technical 7 1286854

Papers on Challenges To High Temperature Operation Of Proton Exchange Membrane Fuel Cells, which disclose a fuel cell using a platinum anode catalyst. A composite membrane based on perfluorinated sulfonic acid (NafionTM) and acid-filled yttrium is mentioned, as well as a sigma/Nafion U.S. Patent No. 6,509,943 discloses solid, inorganic-organic composite membranes for use as ion conducting membranes in electrochemical devices. Examples are based on antioxidant polymer matrices filled with inorganic oxide particles. Organic polymers include polytetrafluoroethylene. Ethylene, perfluorinated sulfonic acid, polyfluorene, etc., and inorganic oxides are heteropolytungstates, ® heteropolymolybdates, anions of cerium and lanthanum, and the like.

Rupich et al., "J. Electrochem. Soc." 1985, 132, 119, entitled "Characterization of Chloroclosoborane Acids as Electrolyes for Acid Fuel Cells", discloses hydrated gas-based closed boron burns, H2B1() C110 and As a replaceable liquid electrolyte for intermediate temperature fuel cells. As described in this reference, aqueous solutions of these acids also exhibit poor oxidative stability and they adsorb more strongly to the pt catalyst than the aqueous solution of sulfuric acid which itself adsorbs strongly to the cathode. All patents cited above are incorporated herein by reference. SUMMARY OF THE INVENTION The present invention provides a proton conducting medium comprising a qualitative (tetra) conductive solution f' for an electrochemical device (e.g., a neon cell) comprising a fluorolactate or fluoroisoborate of the formula:

HaMbQ.nH20 where Η is a proton 'M is a cation, Q is fluoroboric acid or fluoroisobornic acid 8 1286854 ion, and hydrated water is 2 〇) n molecules, which can be any number, or at 0·01 to Within the range of 1000, & varies within the range of 〇〇1 to 2, b varies from 0 to 2, and the ratio of b to a is smaller. The anion may be monovalent or divalent, and the cation may have an oxidation state that varies from +1 to +4, based on which (and in view of the +1 charge of the proton, whether free or = dosed), the subscript & And b make the formula electrically neutral. As written, when the field b is larger than 〇, the formula describes an acid salt, but the present invention includes the case where there is no cation in the formula (i.e., when b = 〇). For the embodiment where b is 〇, a is equal to 1 or 2, respectively (i.e., Q is a monovalent or divalent anion), the composition of the above formula is now a hydrated acid, HaQ.nH2〇. When b is greater than 〇, the proton conducting electrolyte is the acid salt, HaMbQ.nH20. The proton conducting electrolyte of the present invention further comprises an acid HaQ.nH2 hydrazine acid salt, a mixture of HaMbQ nH2 hydrazine. The Q may be the same or different, or a mixture of the same or different acid salts HaMbQ 'nH2 ,, (may be the same or different from and/or Q), or any combination thereof. For the mixture of hydrated acids of the present invention, the average value of a will vary from 1 to 2. The proton may be free (as H+) or one or more water molecules ^σ, for example as a hydrated proton Η3〇+. Helium is any cation that is stable throughout the electrochemical window of the fuel cell. Therefore, the anode should be resistant to hydrogen reduction at the anode of the fuel cell, while the cathode of the fuel cell is resistant to oxidation by oxygen. The σ-compatible cation is an alkali metal (Group 1 in the periodic table), for example, [i, Na K , Cs cations and alkaline earth metals (Group 2 in the periodic table), such as Be, Mg, Ca, Ba, Sr cations) And (in the periodic table) cations of the lanthanides of Group 3 and (in the periodic table), such as Al, Sc, Y, 9 1286854

Ce. In addition, chemical and reduction. Money, tetrabutylammonium tetramethylammonium, ammonium and organic substituted ammonium cations usable. Organic ammonium cations useful in the present invention. Examples of which are also more resistant to oxygen include tetraethyl, triethylammonium, monomethylammonium, and di-sigma rice bran.镔 and are burning base scent. Methylammonium, trimethylammonium, top hydrate, Β σ ^ WaQ nH2〇 k for the highest conductivity. However, the introduction of other acid cations is the control system* = various physical properties (to some extent, conductivity), especially its melting point'

More methods are provided to control the physical state of the proton-named electrolyte under fuel cell conditions. The anion Q can be a polyhedral fluoroborate or a fluoroisobate, such as the exemplified compounds listed in Figure 1. Figure i shows an example of a polyhedral sphere having 12 and ίο vertices for use as a proton conducting electrolyte in the proton conducting medium of the present invention. Alternatively, these proton conducting electrolytes may be 1 〇, 丨丨 or 12 atom polyhedral spheres, containing a boron atom alone or containing a boron atom and another carbon atom in the cage chemical structure of the ciuster. The polyhedral boron ruthenium may carry atoms of fluorine, hydrogen, gas, bromine and/or -OR, wherein R is a ruthenium, alkyl or fluoroalkyl group attached to the boron atom of the sphere. Including three types of anions: (1) a composition (B12FXZ12_X) 2, or a closed borate anion of (B10FXZ1()-X) 2 · where Z is H, Cl, Br or OR, where r is η, alkyl or fluorine Alkyl, and X is based on the average, ranging from 3 to 12, or ranging from 2 to 1 ;; (11) ((R'WJNBnFxZdbx))1 or ((wrrjNBnjFxZp.x) a closed amine borate anion composition of 1 - wherein N is bonded to B and each of R', R", R... is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl 1268654 - and a group consisting of groups; Z is H, Cl, Br or OR, r is Η, alkyl or fluoroalkyl in the basin, and χ is based on the average, varying from 〇 to i 1 or 0 to 9 within the range of changes. (iii) a closed-monocarbonorate anionic composition of the formula (R""CBUFXZ(1)...)1 or (R""CB9FxZ(9 x))1-, wherein R"" is attached to C And a group selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an aryl group and a polymeric group 'Z is Η, Cl, Br or OR, wherein r is η, an alkyl group or a fluoroalkyl group, and X is varied within a range of 0 to π or within a range of 0 to 9 based on the average. In one embodiment, the invention is a proton conducting medium comprising a tantalum anode, an oxygen cathode, and a proton conducting electrolyte, the electrolyte comprising the above fluoroborate or fluoroisoborate. The chemical stability of the polyhedral fluoroborate acids and acid salts of the composition HaMbQ.nH2〇 makes them useful as proton conducting electrolytes in electrochemical devices of any temperature or temperature of 8 〇 3 〇〇〇 c or 12 〇 _ 25 〇 . The proton conducting medium of the present invention is used in electrochemical devices such as fuel cells, water or steam cells for the production of hydrogen and oxygen substantially opposite to fuel cell operation, and for measuring H2 (gas) / H (solid or liquid) Electrochemical potential in electrochemical 仏 sensors = often useful. The proton conducting electrolyte of the present invention contains an acid and a heart salt of a fluoroborate and/or an acid or acid salt of a deuterated isocyanate which provides an advantageous combination of physical, electrical and chemical properties. These compositions can function as solid or liquid protons, suitable for a range of humidity levels and temperatures, including low temperatures, from ambient temperatures up to 25 (medium temperatures of TC. They are suitable as proton conducting electrolytes, On (H2/〇2) fuel cell, 11 1286854; the battery operates in the temperature range of 80 ° C to 250 ° C, or in the temperature range of 150 ° C to 25 0 ° C, where the 〇 2 electrode is more effective And such cells are less sensitive to the poisoning of CO. Some embodiments of the proton conducting electrolyte of the present invention have high conductivity, affinity for water, resistance to reduction (H2 reduction), and oxidation resistance (〇2 oxidation). These embodiments can observe these conclusions when the proton conducting electrolyte is a liquid or a solid. Some embodiments of the proton conducting electrolyte of the present invention are better oxygen than the currently used fuel cell liquid electrolyte (H3p〇4). The solvent, and having better electrochemical performance than h3po4 'allows for higher current densities, and allows the manufacture of fuel cells with high power density. The related applications assigned to the assignee of the present application include U.S. Patent Application Serial Nos. 60/561,193; 10/655,476 and 10/427, the entire disclosure of which is incorporated herein by reference. "Base" means an alkane group which may be derived from an alkane from which one hydrogen is removed. Examples are methyl (ch3-), ethyl (C2H5_), propyl (CH3CH2CH2), isopropyl ((CH3) 2CH_) and a third butyl group ((CH3)3C-.) These alkyl groups may have any number of carbons, or 10 carbons. These alkyl groups may be branched, linear, or contain a ring structure. Cycloalkyl is included in the term "alkyl, unless the alkyl is described as being only branched or straight-chain, but the term "cycloalkyl," as used in this application, describes an alkyl group having at least one ring in the structure. The alkyl group can have any number of carbons, or 4 to 1 carbon, or 4 to 7 carbons. 12 1286854 The term "aryl," as used herein, refers to phenyl, benzyl, naphthyl, ring. Pentyl, decyl or tolyl. The term "fluoroalkyl" as used in this application, refers to the use of fluorine An alkyl group as defined above is substituted for at least one hydrazine. A highly fluorinated fluoroalkyl group means a decyl group in which 60% or more, up to 100% (perfluoro) of hydrogen is replaced with fluorine. For describing the fluoroborate or fluoroisoborate acid or acid salt of the present invention

In the case of a substituent, the term polymeric group,' refers to a polyolefin, poly bond or polyamine, or an aryl or alkyl substituted polyolefin, polyether or polyamine. The term "proton conducting membrane," or "proton conducting medium," is used interchangeably; however, the use of the term proton conducting membrane is not meant to be limiting, but rather it is understood to mean that the proton conducting medium may be in the form of a membrane or may be — a liquid, a gel, a solid, a mixture of a solid and a liquid, or may take any form. The term "proton conductor," or "proton conducting electrolyte," is used interchangeably. The present invention relates to proton conducting electrolytes useful in proton conducting media in electrochemical devices such as fuel cells. In addition to the proton conducting medium of the present invention, the electrochemical device of the present invention generally includes an anode, such as hydrogen hydride: a cathode, such as an oxygen cathode, and a solid or liquid proton conducting: desolvation. This proton conducting electrolyte contains a fluoroboron I salt or a fluoroisoborate acid or acid salt represented by the following formula.

HaMbQnH20 water molecule (H2〇) association, M borate anion. An anion wherein ruthenium is a proton, which is a cation with n hydration, Q is a fluoroborate or fluoroiso 13 13286854. It is monovalent or divalent, and the cation can have an oxidation from +1 to +4. Based on this (and given the +1 φ # of the proton, regardless of whether it is free or solvated), the choice of subscripts 3 and b makes the formula electrically neutral; therefore, a can be 〇.〇 a real number of 1 to 2 and b can be a real number of 〇 to 2, and when 匕 is larger than 〇, the ratio of 'b to a is smaller than just: the embodiment includes that there is no cation (b=G) in the formula, which In the case of ruthenium or 2 (when tQ is known as an anion, respectively), the formula for the gas-depleted acid salt or the oligo-isoformate is HaQ.nH2〇e. The embodiment further includes the following case, wherein protons The conductive electrolyte includes a mixture of the acid like Newton 20 and the acid salt HaMbQ.nH2〇. The molar ratio of acid to acid salt may vary within the range of J 100.1 of the acid salt of the acid salt or within the range of u to 10 ··1 of the acid salt. Protons may be free (as H+) or solvated with one or more water molecules, for example as hydronium ions, H3 〇+. Μ is any cation that is stable over the entire electrochemical window of the electrochemical device. Thus, in most embodiments, ruthenium should be hydrogen-reducing at the anode of an electrochemical device (eg, a fuel cell) and electrochemically Oxygen-resistant oxidation at the cathode of the device (eg, of a fuel cell). The electrochemical reduction potential (E.) listed in the cRc Handbook of Chemistry and Physics, DR Lide (Ed) 74th Ed. on pages 8-21 to 8-31 can be used as a guide for large = (non-authoritative test) Choose the right cation. Thus, a suitable cation may be a cation that satisfies the following conditions: (a) It has a lower (more negative) E to the lower oxidation state than the lower formula of the quasi-tantalum electrode. : E for 2H+ + 2ee = H2. The oxidation of the ions to a higher valence state is prevented by 0 V, and (b) the 14 1286854 ^ ion, wherein the corresponding higher oxidation state of E is compared to the gas reduction of the following acid vehicle. Higher (more)·〇2 + 4H+ + 4e- == 2H. "诂山" period 2ίΪ2〇, where ΕΊ.229 V. The examples are monovalent and divalent cations of each of Group 1 and Group 2, such as Li +, Na+ (for ' 6 Na ' E 疋 -2.71 V) Mg, Ca (for Ca2+ + 2e. = 疋2·87 v)' is also a trivalent cation of group 13, Al3+ (for Al3+ + 3e, ^, £. = -1 67v), and with 3+, etc. The higher cations of Group 2 are unknown and are believed to have a negative E° value to satisfy the criteria (8). Other cations of the other family that meet the ant criteria in the periodic table are decorated with (+3) ions: for ~+ + 3e = Ce, E. It is -2.34 v and for Ce4+.... 3+, e. Yes] 72 and Ming (+2): For CV+ + 2e-, Ε〇=·〇28 v and for c〇3+ + e = c〇2+, E〇= 1.92 V; hammer (+4) ion: For Zr4+ + 4 Bu heart, e. Yes"μ v , give (+4) ions: for Hf4++mm.55V„子: for 2++ 2e· = Ni, with -0.257 V, and for Ni2++ 2H 〇= Ni〇2+4 expansion + 2e_' is MW; and steel (+3) ion, for J3 + + 3e-=La, E. is _2.379 v. However, cations that are not satisfied by both standards can be used as the cation M in this proton conducting electrolyte. The third and fourth alkylidene ions of the formula R3NH+ and R%N+ are either more resistant to reduction and oxidation, respectively, and therefore: used as a proton conducting electrolyte (monovalent) The cation is any alkyl, stupid A and alkyl substituted phenyl. 1 ^ Alternatively, a combination of two or more different cations may be employed, the cationic enthalpy of the proton conductor, such as Li+K+, ca2+:u+ Etc. Although the mass 15 1286854 sub-conduction does not necessarily require the presence of such a cation, the hydration control of the chemical device is used in the present invention. The hydration control of the seed salt provides the heart to be tightly coupled with water. This stronger = ion-matching is very good for maintaining fluidity (when fluidity is required); scheme = proton-conducting electrolyte Mass 8 participates in proton transfer at ^ ^ _. Wenda (higher charge ratio range), less hydrophilic cations (such as Cs+) tend to raise the melting point of the acidate' and obtain a reduced flow of solid proton conductor Composition 'This may be particularly useful for other embodiments, such as non-static fuel cells, such as automotive fuel cells. Group Q may be selected from the fluoroborate (1) and isoflurane (ii) and (in) shown in Figure i Anions, or fluoroborate and isofluorate anions similar to those shown in Figure i. Q can be selected from the following classes: (i) $ (BuFxZ"2.")2-, or (UxZww) a closed borate anion group of 2-, wherein Z is H, Cl, Br or (OR), wherein R*H, affinity or φ fluoroalkyl; x is based on an average, respectively 3 to 12 Change within the range, or within the range of 2 to 1 〇. These compositions are polyhedral spheres composed of 1 or 12 butterfly atoms, each of which is bonded to a hydrogen, a dentate atom, a hydroxyl group or an alkoxy group as defined. Examples of these fluoroborate anions as components of the specific salt MbQ and components of the corresponding acid (HaMbQ) and their methods of manufacture are described in U.S. Patent 3,551,120, Solntsev, Κ·A·, Mebel; A. M.; Votinova, Ν·A·; Kuznetsov, Ν·J· ; Charkin, D· Ρ·; Koord Khim. 1992, 1 8, 34 〇 · US Patent 6448447 Bl; and Serial No. 10/427,341, US Pat. Please, the entire contents of this application are hereby incorporated by reference. (ii) a closed aminofluoroborate anion composition of the formula ((RWJNBuFxZdk)) 1 or ((R'R'TTJNBwFxZ^)) 1- wherein N is attached to B and R', R", R... Each of them is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, and polymeric groups; Z is H, C, Br or (OR), wherein R is fluorene, alkyl or fluoroalkyl And x is based on the average, and varies within the range of 〇 to 11 or within the range of 〇 to 9. These anionic compositions are also polyhedral boron spheres of 10 or 12 boron atoms, one of which is attached to an amino group (^11, 11, 11, 11,), while 卩, 11, <: Or the sulfhydryl group is attached to the remaining boron. Further description of these compositions and examples thereof are found in U.S. Patent No. 6,335,466, the entire disclosure of which is incorporated herein by reference. (out) a closed-monocarbonate anionic composition of the formula (R.-CBnFxZm-x)) 1 or (R, ", CB9FxZ(9_x))i-, wherein R"" is attached to C, And a group selected from the group consisting of a wind, an alkyl group, a cycloalkyl group, an aryl group, and a polymeric group; Z is Η, CM, Br or (OR), wherein the reverse is a hydrazine, an alkyl group or a fluoroalkyl group, and X is based on the average, and varies within the range of 〇 to 丨丨 or within the 〇 to 耗. These fluorinated closed-type carbonate anion compositions are also polyhedral spheres comprising 11 or 9 boron and a single carbon atom. As stipulated above, these borons are partially or fully fluorinated and the carbon atoms are attached to a single organic substituent. These anionic compositions are described in U.S. Patent No. 6,130,357, the disclosure of which is incorporated herein in its entirety. Examples of useful fluoroborate or fluoroisosarate acids and acid salts of the proton conducting media of the present invention include: wherein χ is based on 17 1286854, the average 'is 3 to 12, or 7 to 12; B12(OR)xH12-x2· Wherein R is alkyl or fluoroalkyl and X is based on the average, from 3 to 12, or from 7 to 12; ΒΜηΝ^'ίη'')1-, wherein R, R, and Rm are independently Alkyl, or each ethyl; or B12FXC112_X2· or B12Fx(OR)12-x2·, where x is based on the average and is 3-12, or 7-12. Among the three types of borate anions listed above, the structure of class (1) is a divalent anion, and provides more mass φ than the (ii) and (iii) anions of a = 1 (where a = 2). Thus, the anion of class (1) (all other equivalents) potentially has a higher proton conductivity than the anion of class (1)) and class (iii). Anions of the class (1) are synthesized by one of ordinary skill in the art in accordance with known routes. Synthesis of polyhedral hydridoborates (fluorinated polyhedral borate precursors) See: "polyhedral borane", ELMuetterties and WH κ (10)

Marcel Dekker, Inc. NY 1968. The above (ii) and (Hi) isotonic acid salts have the advantage of being easily functionalized at their nitrogen and carbon atom positions, respectively, as described in U.S. Patents 6,335,466 and 6,130,357 each incorporated by reference. This application. Among these three categories, the fluoroborane (iii) has the weakest compatibility with anions, and thus their protonated form (HQ · nH2〇) should be the strongest acid that means higher mobility, and thus their (Single) protons have higher conductivity. The acid salt of the formula HaMbQ.nH2〇 has a variable number of hydrated water molecules of 1 1000). At the anode and cathode of the fuel cell, this acid salt will balance with both the liquid water and the water vapor. It may be necessary to retain some water to provide a proton transport mechanism for the protons and to provide fluidity if needed. References · Proton Conductors", P. Colomon Ed, Cambridge University Press 1,286,854 / (1992), Chapter 2. Under the operating conditions of the device, the proton conductor electrolyte, HaMbQnH2, can be either solid or liquid. And/or the proton conducting medium may additionally have an inert porous support which acts as a membrane separating the anode and cathode of the device. When the proton conducting electrolyte is a liquid, it is more likely to be used in an electrochemical device. Porous support. It is expected that the liquid proton conducting electrolyte is advantageous because it is expected to have a higher conductivity due to the fact that the protons in the liquid medium are more transportable. In order to obtain a liquid form, the hydration level (n) is sufficiently increased to produce a liquid. Typically, when hydrogen is the only cation, η is 〇, η is at least 6, usually at least 8 and preferably to J 疋 10 and can be as high as 1 Torr depending on the operating temperature and pressure of the electrochemical device. Said that in addition to the additional cation of hydrogen (when b is greater than 〇), it affects the melting point and state of the hydrate. The advantage of a solid proton conducting electrolyte is that The required physical separation between the anode and the cathode of the electrochemical device can be provided by other components. The solid-formed HaMbQ.nH2〇 proton conducting electrolyte can be used in fuel cells. When n is less than 6, a solid form generally occurs. By doping the liquid form of the proton conducting electrolyte of the present invention, such as fluorododecanoic acid (in this case U 〇), with a probiotic cation (eg, M=K+, Ba2+, and/or any other cations listed above), A solid proton conducting electrolyte can be obtained. By adding 1M larger than cerium HaMbQ.nH2 cerate, or an anionic Q cerium (tetra) salt or other known cation source, inorganic cations can be provided to form higher viscosity or solid A proton-conducting electrolyte composition having a higher melting point. Polyhedral fluoro-per sulphonate, HaMbQ»nH2 〇 proton, can be produced by direct fluorination of the corresponding globic boric acid M, such as a polyhedral 1868854 hydridoborate in a liquid medium. Conductive medium. Alternatively, the borohydride precursor of the neutral salt, MbQ, can be fluorinated in a liquid medium and subsequently subjected to acid metathesis. The replacement cations are described in the following Examples 3 to 5. The partial exchange of the proton pair MbQ_nH2〇 results in the acid salt having the following structure: HaMbQ'nl^O. By introducing the fluoroborate directly with these halogens, introduction Other halogens, C1 and Br, are added to these fluoroborates. _ In the direct fluorination of the proton conducting electrolyte of the present invention, the fluorine is diluted with an inert gas, for example with nitrogen, so that the fluorine concentration is 1 〇 0 / 〇 of the total gas volume. Up to 40%. The liquid medium or carrier used in this borohydride does not substantially react with fluorine. One conventional medium is liquid hydrogen fluoride, HF. Other liquid media can be used in this process, and it includes water, organic acids For example, formic acid, acetic acid, trifluoroacetic acid, and the like. The acidity of such liquid media, particularly in hydrogen. Boron fluorination, can affect the solubility of the precursor borohydride and fluorinated borohydride and affect the change in acidity therein. Preferably, the medium is designed to maintain both the product of the borohydride and the hydrogen fluoride borate in the solution of the medium. A radical scavenger can be used in the fluorination process to reduce by-product formation and increase reaction efficiency. In aqueous solution, a radical scavenger is present to limit the formation of cerium peroxide or HOF, which can be produced under the action of fluorine. A radical scavenger is used in the case of using an organic acid such as formic acid. The thiol-based purifying agent suppresses the side reaction of fluorine and solvent, and therefore, the fluorination efficiency is improved. Examples of the radical-based scavenger include oxygen and a nitro-substituted aromatic compound. A small amount of air is introduced into the liquid medium, which removes the free radicals produced by the direct fluorination of the hydrazine borate 20 1286854 (hydridodoborate) salt. Fluorination of the polyhedral borohydride anion can be carried out over a temperature range sufficient to maintain liquid phase conditions. In order to fluorinate polyhedral borate anions, the temperature is controlled at 30~i〇 (TC, typically 〇-2 (rc. The pressure during fluorination is such that the liquid phase conditions are maintained, typically atmospheric pressure. Various reaction conditions and reagents are available) Stoichiometric control of the degree of fluorination of polyhedral borohydrides and the degree of fluorination of borate. To prepare a hybrid halogen fluoroborate (Q, where Z is C1 or Br; or C1 or hydrazine and H), part of the fluorine The product is reacted with Ch or Bq. Additional descriptions and examples can be found in U.S. Patent No. 355,112. A closed borate comprising an OH substituent can be prepared by treating a polyhedral hydrogen-closed-borate with 40% sulfuric acid. It is described in Peymann, T.; Knobler, CB; Hawthorne, M. R Inorg. Chem. 2000, 39, 1163, which is incorporated herein by reference. It can form hydrated fluoroborate acid HaQ.nH20 from fluoroborate (where n is at least 1, preferably at least 5, and more preferably η is at least 8 to ι 〇〇〇). Φ A method comprising: treating an aqueous solution of barium salt BaQ or BaQ2 with sulfuric acid or with an aqueous solution of HF, or calcium salt CaQ or Aqueous solution of CaQ2 And removing the insoluble salts BaS〇4 and CaF2 by filtration. The water is removed from the aqueous solution of the hydrated fluoroborate until the desired acid/water ratio is obtained. As a proton conducting electrolyte used in the electrochemical device, the present invention has the formula HaMbQ The acid or acid salt of fluoroborate or fluoroisosarate of .nH20 can be used alone or as a solution, suspension or mixture. The mixture is in combination with one or more other fluoroborates or fluoroisolated salts. Formed by acid or acid salts (having different enthalpy and/or Q definitions), and/or may be mixed 21 1286854 to form a solution, suspension or a mixture with other (type) proton conducting electrolytes. Examples of other proton conducting electrolytes of the proton conducting electrolyte combination of the present invention include: anhydrous phosphoric acid, alkanesulfonic acid, fluoroalkanoic acid, or sulfuric acid, or a combination thereof, to produce a desired proton conducting electrolyte. Fluoroborate or fluorinated a mixture of an isoborate acid or an acid salt with an acid, or a mixture with another proton conducting electrolyte, whether the fluoroborate is in a liquid or solid form, It can be used in a wide range of complexities. Typical ratios in proton conducting media are from 0.01:1 to 10:1 parts by weight of bismuth borate or fluoroisoborate proton conducting electrolyte to parts by weight of phosphoric acid or other protons. Electrolyte. A fluoroborate or fluoroisobate proton conducting electrolyte in solid form can be used as an additive of the present invention to modify the melting point of these mixtures as needed. Acids and acids of fluoroborate and fluoroisobinate Salts, either as a mixture or alone (with or without other proton conducting electrolytes), can be blended with various polar functional group-containing polymers to form a composite membrane that can be used as a proton conducting medium in electrochemical Φ devices. This blending is accomplished by allowing the polymer to absorb a solution of the fluoroborate or fluoroisoborate acid and/or acid salt formed in a solvent. The solvent is, for example, a polar organic solvent such as N•methyl. 11 各 or acetonitrile' then remove at least part of the solvent from the obtained composite. Or casting a polymer membrane proton conducting electrolyte with a solution containing one of the polymer and the acid or acid salt of the fluoroborate or fluoroisobinate (with or without other proton conducting electrolyte) in a mutual solvent. Or a variety. Polymers suitable for forming a composite film may include: polymerized perfluorosulfonic acid, ethylene tetroxide, polyaniline, poly. In general, polymers containing a polar group of a charcoal 22 1286854-group, amine, ether, sulfone or hydrazine can be used, which are expected to interact with protons or metal cations of the electrolyte. Preferred are nitrogen-containing or oxygen-containing polymers, such as polyethylene bitumen, polyaniline, polybenzazole, polybenziminazole, polybenzopyrene, sigma, etc., wherein an expected nitrogen or oxygen is desired. Interacting with the proton conductors makes it easy to form a suitable two component blend. An additional embodiment of a useful polymer is disclosed in U.S. Patent 5,525,436. The liquid proton conducting electrolyte of the present invention may be impregnated into a porous substrate, for example, impregnated onto a porous substrate containing microglass fibers, tantalum carbide, boron nitride or a porous carbon material, thereby forming a proton conducting medium further comprising a Battery separator. A physical mixture of the solid proton conducting electrolyte of the present invention with a porous matrix such as microglass fibers, tantalum carbide, boron nitride or a porous carbon material may also be employed in the electrochemical device. • The operating temperature range of the electrochemical device can be any range, or 120-220 ° C, or 150-200 ° C. • The proton conductor of the present invention can be used in any device in which & (gas) and proton source are electrochemically balanced. This is one of the basic processes in fuel cells. A proton conducting electrolyte may also be employed in the hydrogen sensor device, wherein the partial pressure of helium is a function of the potential measured on the electrode in contact with the proton conducting electrolyte. In addition, proton conductors can be used to generate the electrolysis of the 〇2. Optionally, higher electrochemical efficiencies can be achieved at higher temperatures in the presence of steam; these devices are essentially the opposite of fuel cells. · References · "Proton conductors", op. cit., Chapter 32. For more information on fuel cells and their components, see: AJ Appleby; FR Foulkes 23 1286854, Fuel Cell Handbook, published: New York: Van Nostrand Reinhold, ©1989 〇 for illustrative purposes of the various embodiments of the present invention The following examples are provided, and the examples are not intended to limit the scope of the invention. Example 1 Preparation of [Et3NH]2B12FxH12-x (x=l〇,11, or 12) $10%F2/1〇%〇2/8〇%N2 (% by volume) of a gas mixture fluorine at 20C

2.01 g of a slurry in 10 g of glacial acetic acid. Add a total of 116 mmol F2 (22% excess). The slurry remained colorless throughout the fluorination process from the beginning to the end, while its viscosity was never observed to reduce the complete dissolution of the solid. The oxidant iodide test of the product slurry was negative when fluorination was completed. It is then emptied and the crude product is dissolved in water. Triethylammonium hydrochloride (24 〇 mm 〇 1) was added with sufficient diethylamine to bring the pH of the solution to 5. The product was filtered, washed with water and dried. 0.32 g (65% yield) of fluoroborate salt was isolated. 19F • NMR analysis showed that Bi2f10H22-(7%), B12FlrH2-(18%) and (75%) had only traces of hydroxyl substituted impurities. This crude reaction product was dissolved in water and the pH was adjusted to between 4 and 6 with triethylamine and triethylamine hydrochloride. The precipitated product was recrystallized, filtered under vacuum and dried at 100 °C. Example 2 Defluorination of K2B12H12 in formic acid (15% concentration; addition of hydrazine 2) In this example, as described in Example 1, fluorination in 1 mM of formic acid at 0 to 1 °C 1.8 g (7.2 mmol) of Κ2Β12Η12· 24 1286854 C Η 3 Ο Η 益 、 、 、 、 、 、 ° ° ° ° ° ° ° ° ° ° ° ° 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 After the gasification process is dissolved, the end of the fluorination, the colorless, homogeneous solution is obtained. 1% = 2 crude product solution analysis shows that it is mainly Bi2FuH2. (35% ^

Bl2Fl22_(6〇%) and about 5% of the mono-based impurity BMnOH. No (four) dimer impurities. The triethylbenzene was removed as described above, the product was isolated, and the above fluorinated borate ball product was obtained in a yield of 80%. Example 3 Direct fluorination of ruthenium 2Β12Η12·ηΗ20 Preparation of H2B12F12.nH2 〇 -15 C with 2% 〇/〇 solution of 20% F2 fluorinated HF in N2, providing other anions (byproducts) content from low BuFu2- . Based on the i9F NMR spectrum of the crude reaction mixture, the molar ratio of anions was: B12F122-(1), b24F224-(001), Bi2Fii(〇H)2.(〇〇5) and BF4_(0.36). About 3 moles during the reaction. / Bi2f122-decomposition of hydrazine produces a molar ratio of BF4j B12F122- 0·36. Thus, the yield of h2b12F12·ηΉ2〇 in the above reaction is close to 90%. Example 4 Preparation of a highly fluorinated hydroxy-substituted borate ball salt A colorless slurry containing about 4.0 grams (17 mmol) of K2B12Hn(OH) was prepared as described in U.S. Patent 3,551,120, the disclosure of which is incorporated herein by reference. This was dissolved in 15 ml of citric acid and treated with 10% F2/10% 02/80% N2 (240 mmol of F2 total, 27% excess) at -10 25 1286854 • to -5 °C. Analysis of the crude product by 19F NMR showed mainly b12fu(?h)2-(55%:^B12F1()H(OH)2-(35%) and about 5% of dihydroxy impurities. Example 5 Preparation of highly fluorinated A hydroxy-substituted borate ball salt is prepared as described in U.S. Patent 3,551,120 to prepare a colorless slurry containing about 2.2 grams (7.87 mmol) of Β2Β12Η10(ΟΗ)2, dissolved in 8 ml of formic acid, and 10% F2/ 10% 02/80% N2 (a total of 114 mmol of F2, 30 〇 / 〇 excess) was treated at _1 Torr to -5 ° C. Analysis of the crude product by 19F NMR showed mainly b12f1q (〇h) 22-(30 %) 和政1: ^ 911 (011) 22 - (60%) and about 10% of trihydroxy impurities. Example 6 Preparation of (H30) 2B12FxH12.x, χ = 10, 11 or 12 Solid Ba(OH) 2 · 8Η2〇 (2·53 g, 8·0 mmol) was added to [Et3NH]2[Bi2Fi2] (4.50 g, 8.0 mmol) in 50 ml of water in suspension _ in 'under reduced pressure Diethylamine was distilled off. After removal of triethylamine, an aqueous solution containing BaB12F12 was formed. The aqueous solution of BaBl2Fl2 was treated with an aqueous solution of h2S04, and the precipitate of BaSCU was removed by filtration. Water was distilled off from the filter cake and dried at 190 ° C under vacuum. Solid 2 hours. For this The solid was subjected to thermogravimetric analysis. The solid (〇·211 g) was dissolved in 1 ml of water and treated with Ph4PC1. The formed white sink was washed with water and dried under 12 Torr for 2 hours to collect 545·2. [Ph4P]2[B12F12] (the amount of [Ph4P]2[B12F12] collected for H2b12Fi2 · 2Η2〇 should be 550.5 mg, and the amount of [Ph4P]2[Bi2Fi2] collected for H2Bi2Fi2.4h2〇26 1286854 should be It is 504.6 mg). According to the thermogravimetric analysis, the composition of this solid acid is H2Bi2Fi2 ·2Η2〇. The infrared spectrum of this solid acid gas-carbon full/bone soft cloth contains one at 3〇84 cm·1. Wide and strong OH stretching, a lower strength OH stretch at 3269 and a h〇H band at 161 〇cm·1, all belonging to the (H3O) cation. It is expected that samarium and calcium can be treated similarly with sulphuric acid. The 0 salt of fluoroisofluoroborate is used to produce a hydrated acid of isoflurane, such as H (R "'CBllFxZ("-x)).nH2〇 and HaRUlNBuFxZn.O.nHsO. A conventional method having a polyhedral borate anion produces the above acid 'which includes a H+ shape An ion exchange column is used to elute the anion salt and the water is removed under reduced pressure. However, contrary to the procedure of this embodiment, that method may be time consuming and may require evaporation of large amounts of water. It may also cause the product acid to be contaminated with organic impurities. φ Example 7 Determination of stability of (h3o) 2b12f12 under humid air conditions This example shows that the acid under inert atmosphere (HsOhB^Fi2 is stable and low in water vapor at up to 250 ° C under humid air conditions) Under Lili (in this case only 24 Torr) this acid absorbs water at 25 ° C, which is an important feature of electrochemical devices such as fuel cells. The solid acid prepared as described above is exposed to air for 18 hours. Thermogravimetric analysis (TGA) of this acid was carried out in dry hot air. To determine the water absorption under these conditions, the air flow was switched between dry air and moist air (air bubbles passing through the water at about 25 ° C). The result of the knot 27!286854 is shown in Fig. 2 - Fig. 4. As shown in Fig. 2, it is heated from 25 ° C to 22 in a dry air atmosphere (Γ: the obtained result is not significant, the solid weight loss is 20.75 ° /., This corresponds to the conversion of h2B12F12·8H20 to 2H2〇. This composition is stable under an inert atmosphere of 22 〇t, but at 24 Torr water vapor pressure (about 〇1% relative humidity), its composition changes to As shown in Figure 4, this essay is also stable at 250 C at this temperature. Underneath, it adsorbs less water. As shown in Figure 3, when the temperature range is 12〇_ 2〇〇〇c and the water vapor pressure is 24牦, the composition of this solid acid is Η2Βι2Ρι2·4Η2〇. The solid composition did not exhibit any weight loss when it was heated at 20 (TC wet air for 10 hours. In summary, under these test conditions, the composition was substantially free of weight loss, thus indicating the exceptional water storage capacity of this acid. In addition, during the test, there is no evidence to show that the acid HaB^F 2 · ηΗ20 is hydrolyzed or decomposed. φ Example 8 Determination of hydrogen stability at high temperature HzB^F^.nHzO at 200 °C Heating acid H2B12F12.2H20, and H2B12F12.nH20 (n less than 100) with a mixture of 5% Pt on carbon (approximately 5/1 by mass ratio) for 14 days, 100°/. at 50 psig (at 25 ° C) and at 225 psig water vapor pressure The fluoroborate anion is stable according to the 19F and UB NMR of the acid solution. In summary, the acid such as KbB^Fu.nl^O has exhibited stability to hydrogen at temperatures up to 2 。. US Patent 6,468,864 It is shown that solid acid proton conductors based on CsHS04 will be emitted at these temperatures under a hydrogen atmosphere. Degradation 28 1286854 Example 9 Determination of the conductivity of H2B 1 2F 1 2 · nH 2 〇 in water This example shows H 2 B 12 F 12 · η Η 20 as a liquid proton conductor at 20 to 200 ° C at a pressure above 250 Torr. Conductivity. The acid is placed in a glass tank, which is connected to the reservoir via a heated tube. The system is placed under vacuum and the water temperature of the reservoir is changed to change the water vapor pressure within the system, which is also measured by a vacuum gauge. . At temperatures between 20 and 200 ° C, the acid is a liquid (η is equal to 8) and the water vapor pressure is above 250 Torr. The conductivity of the liquid acid was measured using a RadiometerTM CDM21(R) conductivity meter and a two-pole CDC741T conductivity cell. The conductivity cell was calibrated with a KC1 solution. The results are shown in Table 1 〇 Table 1 Temperature, °c Relative Humidity, % Conductivity, mS/cm 120 14 355 — 152 5 307 163 4 283 ~ Conductivity of liquid HzB^Fwnl^O composition Water vapor pressure 200 Torr.

The results in Table 1 show that the composition stores water under low humidity and the conductivity is reduced little. This test relates to the transfer of protons between electrodes of an electrochemical device such as a fuel cell. It is desirable to have a minimum of at least 100 to 150 ms/em, and these compositions clearly exceed this conductivity level. The acid stores enough water to maintain the liquid phase at the same 2 〇〇 c when the water vapor pressure is only 250 Torr. This property is significantly different from the behavior of the gaseous borate acid H2Bl2C1i2.nH2〇 similar to 29 1286854, which cures above 145 and has a water vapor pressure of 6 Torr. This acid, at lower humidity levels (water vapor pressure of 2 Torr), also shows a higher conductivity than the conductivity of 2 (up mS/sm at 6 Torr). 〇mS/cm). Example 10 Mixture of fluoro-saponin acid and anhydrous linalic acid The purpose of this example was to demonstrate that a mixture of fluoroboric acid and anhydrous phosphoric acid forms a melt which still has a high proton conductivity even under an inert atmosphere. Prepare a solid mixture under an inert atmosphere: (H30)2B12F12/2H3P〇4 (about 67% by weight of (h3〇)2b12Fi2), (H30)2B12F12/4H3P04 (about 50% by weight of (h3〇)2b12F12) and (H30) ) 2B12F12 / 12H3P 〇 4 (about 25 weight 〇 / ^ (H30) 2B12F12). These mixtures were heated at 60 to 14 Torr under an inert atmosphere and formed a clear solution at all φ portions above l〇〇〇c. 1 The mixture melt crystallizes at about 1 °C. The conductivity of these mixtures (melts) under an inert atmosphere is shown in Table 2. Table 2 Conductivity composition of phosphoric acid/fluoroborate acid mixture in an inert atmosphere at 100 ° C, Celta conductivity, mS/cm 1 (H3〇) 2B12F1, / 12 H3PO4 1 190 1 (H30) 2B12F12 / 4 H3PO4 96 1 H2B12F12 ·6Η9〇/ 4 Η3Ρ04 179 1286854 ; significantly increase the conductivity of the mixture (melt) by adding a small amount of water. Example 11 High Temperature Stability of Phosphoric Acid/Fluoroborate Acid Mixture The purpose of this example was to determine the thermal stability of a phosphoric acid/fluoroborate acid mixture (melt). (H30) 2B12F12/2H3P04 (about 67% by weight of (HsOhBuF^) mixture was heated under an inert atmosphere at 200 ° C for 20 hours. $ Only 0.2% of weight loss was observed, and according to 19fnMR of this acid solution, The anion is stable. Example 12 Oxygen Reduction Kinetics of an Aqueous Solution of a Mixture of Fluoroborate Acid and Phosphoric Acid The purpose of this example was to determine the oxygen reduction kinetics of a fluoroboric acid aqueous solution, and a mixture of fluoroboric acid and phosphoric acid. CH Instruments Electrochemical Workstation • Record the linear sweep voltammetry of the aqueous acid solution at 1400 rpm on a BAS rotating disk electrode instrument for potentiostats. Saturate the acid solution with at least 1 atmosphere of pure 〇2 before performing the potential scan. 15 minutes, and continuously purged with 02 during the measurement. Several circular voltammetric scans were also applied between 1〇 and _〇·2 V to collect traces of electrical activity in the system before collecting linear scan data. Impurity. The working electrode is a rotating disk electrode that is polished, washed with distilled water, and dried before each new acid solution is measured. It is an Ag/AgCl electrode and uses a pt-wire wound electrode counter electrode. 31 1286854 - The graph of Figure 5 shows that compared to an aqueous solution of pure scaly acid, the hydrated gas is a carbonate acid and a mixture thereof with phosphoric acid. Shows better oxygen reduction power. The proton conducting electrolyte of the present invention also provides a higher current when the potential is the same. By converting to oxygen to increase the negative potential, this shows strong anion absorption. Overpotential and larger Distance-dependent, which is required for the electrons to migrate through the thicker absorber layer interface and interfere with the absorption of the reactants on the electrode. Linear scan voltammetry of the dilute aqueous solutions of spring H2BuF 12 and H3P〇4 shows that 〇2 The reduction potential has a +01 V shift to the former, and compared with H3p〇4, the uy-anion adsorbs less to the platinum catalyst than the phosphoric acid even in the dilute solution. To be much larger, such as 60% η3Ρ04 (aqueous solution) and 6〇〇/0 h2S04 (water rolling) compared to a 6% aqueous solution of 1.1 (wt%) and H3P〇4 mixture, 〇2 reduced The beginning is almost low. 2 V. 1:1 (% by weight) H2Bi2Fi2* The 60% aqueous solution of the H3P04 mixture is almost three times higher than the 60% H3P〇4 (aqueous solution) at the same potential, which indirectly indicates that In the solution of fluoroboric acid, the solubility of oxygen is higher. In summary, the solution of the fluoroborate acid proton conductor has better oxygen reduction kinetics than the pure phosphoric acid solution on the platinum catalyst. The kinetics should lead to electrochemical devices, for example The fuel cell has a higher power density. Also, when used as a proton conducting electrolyte, the resulting mixture shows less adsorption than the pure acid-filled opposite electrode. Example 13 32 1286854 Preparation of proton conductive solid membrane from fluoroboric acid The purpose of this example was to confirm the preparation of a proton conductive solid membrane from fluoroboric acid as a proton conducting electrolyte. A glass fiber paper disc (about 125 microns thick, about 10 mm in diameter, 55 mg) was soaked in a 3% (H3) 2Bl2Fl2 solution for 15 minutes. When the disk was dried in an oven at 12 ° C for two hours, a film having a thickness of 55 μm and a weight of cut (about 90% by weight of solid acid) was obtained. When the glass fiber disk was immersed in about 1% by weight of (H3〇) 2Bl2Fi2 solution, and the disk was dried at 120 °C for 2 hours, a film of 225 μm thick and weighing 8 mg was obtained. In order to measure the conductivity, a film dried at 120 ° C for 2 hours was pressed between two gold discs, and an alternating voltage (amplitude 1 〇 mV) varying in frequency between 0.1 Hz and 0.1 MHz was applied to the film. , measure the complex impedance and record it in Figure 6. The impedance spectra were measured according to the method of X. Qian, N. Gu, Z. Cheng, X. Yang, E. Wang, S. Dong., J. Solid State Electrochemistry, 2001, 6, pp. 8-15. The impedance of the film is obtained by extrapolating the impedance data to the real axis on the high frequency side. At 27C, the impedance of the '550-gas film is 30,000 ohms (conductivity is about I: S/cm), but at 182 °C, the impedance is reduced by 3 ohms to 23 ohms (conductivity is about 1 _6 mS/cm). EXAMPLE 14 This example demonstrates the preparation of a proton conducting solid membrane from a fluorinated closed-isoborate acid. A mixture of compound CS (CBuFllH) (0.3 g) and [N(C4H5)4] [CBuFuHKO.5 g) was dissolved in a mixture of 30 ml of methanol and hexane 33 1286854. The column was filled with Amberlyst-15 cation exchange resin, the composite mixture was diluted, and the liquid fraction was collected in the form of its acid. To the column fraction was added 10 ml of DI water, and the solvent was removed from the diluted solution by vacuum. The remaining acid was dissolved in 5.0 ml of water. A glass fiber paper disk (about 125 microns thick, about 20 mm in diameter, and weighing about 2 mg) was soaked in a solution of fluorinated closed-isoborate. After drying at l2 〇 ° c for 2 hours, it was obtained to contain about 50 wt ° /. Acid and a solid disc of about 50 wt% glass fiber. When the glass fiberglass paper disk was immersed in a more concentrated acid solution and dried at i2〇〇c for 2 hours, a solid disk containing about 90% by weight of acid was obtained. A glass fiber disc containing a vaporized isolateral acid HCBiiF^H · nH2 轻 was lightly pressed between two 15 x 〇.5 mm stainless steel discs at 12 Torr. Dry for 24 hours. The solid film of the fluorinated isoboronic acid has a thickness of 〇.37 mm. The membrane module is sealed into a button cell. Heat the buttons to different temperatures and measure the impedance of these films by impedance spectroscopy. The complex impedance data is extrapolated to the real axis on the high frequency side, see Figures 7 and 8. The conductivity of a film consisting of about 50/50 wt% glass fiber and fluorinated closed isocyanate acid: 0.5 pS/cm at 22 ° C, l〇 (TC 〇 · 02 mS / cm, 112 〇 C 0.04 mS/cm, and ι·ι mS/cm at 140 ° C. The conductivity of a film consisting of about 10/90 wt% glass fiber and fluorinated closed-isobornate is about the same at room temperature However, it is much higher at high temperatures: 0.7 pS/cm at 22 C, 0.47 mS/cm at 120 C, and 3.5 mS/cm at i45 °C. These examples show the use of HaMbQ.nH20 polyhedral fluoroborate and fluorine. Such an advantage can be obtained by using an isotonic borate as an electrochemical device comprising a proton conducting 34 1286854 电解质• electrolyte in a fuel cell. Some embodiments of the proton conducting membrane of the present invention are liquids having a lower volatility and a lower viscosity; Embodiments are solids having low volatility and high viscosity, which can be used as a separator between the cathode and anode of the electrochemical device, if desired. Some embodiments are, for example, 0-250X:, 80-250 ° C, 120- 22CTC or 150-20 (TC any temperature is hydrophilic and can be packaged 15〇_ 25 (any temperature of rc operates the electrochemical device, in which the platinum catalyst Φ commonly used for anodes is less sensitive to c poisoning. Many of the proton conducting electrolytes of the present invention provide oxidation resistance at operating temperatures (being 〇 2) and resistance to reduction (and; and / or weak adsorption of platinum anodes, can make the current density obtained in some electrochemical devices higher. In addition, other embodiments of the proton conducting electrolyte of the present invention are generally good oxygen The solvent can be used to obtain higher current densities. The invention has been described with reference to the specific embodiments, which are not to be construed as limited by those skilled in the art. Modifications of the embodiments are included. These equivalents are included in the scope of the present invention. All references, patents and patent applications cited herein are hereby incorporated by reference in their entirety in their entireties in After the reference, there is no such statement or similar statement. The schematic diagram briefly shows that the structure of the fluorinated closed borate of Figure 1 is shown in column (1). The structure of the closed water (tetra) stone is shown in column (9), and the structure of the closed monocarbonate is shown in column (in), which is used in the electrochemical device/proton conducting medium of the present invention. The gas atom (F) can be substituted with other groups 35 1286854 hydroxy, alkoxy and this group (Z), which include hydrides, other groups described in other halogen applications. Figure 2 shows H2B12F12 ηΗ20 at 220 ° C t Thermogravimetric analysis (TGA) of the gas flow conditions. Figure 3 shows the thermogravimetric analysis (TGA) of lUuFu.nHzO at 200 °C in dry gas. Figure 4 shows the thermogravimetric analysis (TGA) of H2B12F12.nH20 at 250 °C under dry and wet gas flow conditions. Figure 5 shows a linear disk volt-ampere curve of a rotating disk electrode (RDE) at an aqueous solution of each acid at 14 rpm: a) an i8 (0.5 Μ) solution of H2Bi2Fi2; b) 5 wt% of H3P04 ( 0·5Μ) solution; c) 60 wt% solution of 1/1 mixture (by weight) of H3p〇4 and H2B12Fi2; d) 60 wt% solution of H2S〇4, and e) 60 wt% solution of H3PO4. Figure 6 shows the impedance curve of a glass fiber/fluoroborate proton conducting membrane in an electrochemical device at 182 °C. Fig. 7 shows an impedance curve of an electrochemical device containing a proton conducting membrane composed of about 50 wt% of glass fibers and about 5 wt% of fluoroisocyanuric acid (HCBnFnHTiHzO). Figure 8 shows an impedance curve of an electrochemical device containing a proton conducting membrane composed of about 10 wt% of glass fibers and about 9 wt% of fluoroisocyanuric acid (HCBuFnH-nlO). 36

Claims (1)

Ϊ286854 X. Patent Application Range: 1. A proton conducting medium for electrochemical devices, which contains a proton conducting electrolyte of the following formula: HaMbQnH2〇', a proton in the proton, M is a cation, and Q is a fluoroborate Or a fluoroisoborate anion, η is in the range of 〇.〇1 to 1〇〇〇, a is in the range of 〇〇ι to 2 and b is in the range of 〇 to 2, & It is chosen such that • 弋 is electrically neutral, and when b is greater than 〇, the ratio of b to a is less than 1〇〇:!. 2. A proton conducting medium as claimed in claim 1 wherein further b is 〇 and & is 1 or 2. 3. A proton conducting medium as claimed in claim 1 further comprising a mixture of HaQ.nH2(R) and HaMbQnH20. 4. The proton conducting medium of claim i, further comprising a mixture of HaQ nH2〇 and HaMbQ.nH2〇 having a molar ratio of 1:10 to 100:1. • 5. Proton conductive media as claimed in item 1 of the patent, in which barium is selected from Group 1, Group 2, Group 3, Group 13 elements and actinides, as well as cobalt, zirconium, hafnium, nickel and ammonium and organically substituted ammonium. a group of cations. 6. The proton conducting medium according to claim 1, wherein the cerium is selected from the group consisting of tetraethylammonium, tetrabutylammonium, triethylammonium, monomethylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, A group consisting of imidazole rust and n-alkylimidazolium. 7. A proton conducting medium as claimed in claim 1, wherein the group is selected from the group consisting of Li, Na, cesium, Cs, Mg, Ca, Ba, Al, Zr or a combination of these elements. .. 37 •1286854 and each of R', R", R'" is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, and polymeric groups; Z is H, Cl, Br Or OR, wherein R疋H, alkyl or gas-burning group' and X is based on the average, ranging from 〇 to 11 or within the range of 〇 to 9; (iii) Formula (R""CBllFxZ(1)_x))" or (R""CB9FxZ (9 x) wide closed-monocarbonorate anionic composition, wherein R", is attached to C, and Selecting a group consisting of hydrogen, an alkyl group, a cycloalkyl group, an aryl group, and a polymeric group, Z is Η, α, Br or 〇R, wherein the ruthenium is an anthracene, an alkyl group or a fluoroalkyl group, and the ruthenium is based on The average number is in the range of 〇 to u or in the range of 0 to 9. 15·If the proton conducting medium of patent application 帛1, let Q be, and (B12FXZ12-X) Or (Bi〇FxZi〇x) 2_ of the closed type (d〇s 〇 侧 酸盐 anion, where Z is Η, α, Β 4 〇 R, its towel, alkyl or fluoroalkyl' and X is based on average The number is in the range of 3 to 12, or in the range of 2 to 10. ·16· Please use the proton conductive medium of the first item (4), where 12 12 or Bl2FxHl2-x 'where X is based on The average number is 3-12 Bl2(OR)XHi2-x2- or B12F (0R, 2. Gans 0 η Α , ^ 0 # 2 X(〇R)12_x, where is the alkyl or fluorotext X soil The average is; and R Each of '" is independently selected from the base - ... based on an average of 3 - 12; the group consisting of ~ 1 7. If the patent is applied for 2. The proton conduction medium surrounding the first item, Μ 'The proton is passed through 18. An electrochemical device containing a f-substance medium 39